Nanocomposites of Polyaniline as Conductive Adhesives

Electrically conductive adhesives are emerging as the best possible alternative to traditional tin/lead soldering. In this work polyaniline (PANI) as powder and as nano-fibres was introduced as filler into epoxy/anhydride matrix to produce isotropic conductive adhesives (ICAs). PANI nano-fibres show uniform dispersion and thus percolation threshold is low. Uniformity and smaller size of nano-fibres help in formation of a strong epoxy network with least hindrance from filler phase. This results in better impact performance of these ICAs. SEM observations show an improved diffusion of nano-PANI into the epoxy matrix. Overall, the properties obtained with PANI nano-filler show a significant improvement when compared to PANI powder of macroscopic dimensions.     

The effect of chemical modification on the fracture toughness of montmorillonite clay/epoxy nanocomposites

The change in fracture toughness and its dependence on the content of clay nanoplatelets and adhesion at the interface between clay nanoplatelets and anhydride-cured epoxy matrix are discussed. Three clay nanoplatelets with different chemical modifications were used in this investigation. To fabricate nanocomposites, the clay nanoplatelets were sonicated in acetone for 2 h. The role of the clay nanoplatelets in the mechanical/fracture properties was investigated by transmission electron microscopy (TEM). Bright-field TEM micrographs showed excellent dispersion of clay nanoplatelets in epoxy matrix. Both intercalation and exfoliation of clay nanoplatelets were observed depending on clay modification. Compact tension specimens were used for fracture testing. The fracture toughness increased with increasing clay content. The fracture toughness of clay/epoxy nanocomposites varied with the clay morphology in the epoxy matrix. Different morphologies of the fracture surfaces, highly dependent on the morphology of dispersed clay nanoplatelets, were observed using environmental scanning electron microscopy (ESEM). The fracture toughness was found to be correlated with the fracture surface roughness measured by confocal laser scanning microscopy (CLSM).     

Use of polyethyleneimine dendrimer as a novel graded-modulus interphase material in polymeric composites

The effectiveness of polyethyleneimine (PEi) dendrimer as a novel graded-modulus interphase material in polymeric composites is discussed in the context of core (polystyrene)–shell (PEi) nanoparticles affecting the mechanical properties of epoxy. The dendrimer is grafted onto the surface of polystyrene (PS) particles via a free radical polymerization reaction of styrene monomers in a non-aqueous polar solvent with t-butyl hydroperoxide (TBHP) as initiator and mild heating. The effects of both particle loading and core/shell composition are investigated. The mechanical test results in all cases show an increase in both stiffness and fracture toughness or the ability of the polymer to resist crack growth, as opposed to the commonly seen trade-off between these properties in previously studied soft particles. SEM micrographs suggest that the crosslinks with epoxy in the dendrimer network, leading to a dramatic interface stretching as the core-to-shell ratio decreases, and the capability of the dendrimer to 'harden' PS particles by diverting cracks through them are responsible for the enhancements.     

Surface Energy of Modified Nanoclays and Its Effect on Polymer/Clay Nanocomposites

Surface properties of thermally stable phosphonium-modified montmorillonite were investigated at both room temperature and 220°C. These properties were compared with those of pristine and ammonium-modified montmorillonite. Surface properties at room temperature were calculated from contact angles measured using sessile drops. Several liquids with known polar and dispersion components of surface tension were used. Surface energy of nanofillers at 220°C was calculated from contact angles, using sessile drops of polymer melts. Two commercial polystyrene (PS) resins, with different melt flow characteristics, and high-density polyethylene (HDPE) were used. Isothermal TGA experiments were used to determine the thermal stability of the resins and nanofillers. The dispersion behavior and mechanical properties of the nanocomposites are correlated with the values of the Hamaker constant and thermodynamic work of adhesion for these polymer–nanoclay systems.     

Effect of the physical and mechanical properties of epoxy resins on the adhesion behavior of epoxy/copper leadframe joints

In this study, the adhesion strength of three epoxy resins, which are used as basic materials for epoxy molding compound (EMC) in microelectronics, to copper leadframe was determined using the peel test. The epoxy resins used were O-cresol Novolac (OCN), dicyclopentadiene (DCPD), and biphenyl sulfide (BIPHS) epoxy resins. It was found that DCPD showed the highest peel strength and OCN had the lowest value. The difference in the peel strength was explained by investigating the physical and mechanical properties, as well as the surface properties of the epoxy resins. These properties included the surface energy, viscosity and gelation time, fracture toughness, and the coefficient of thermal expansion. As a result of the lower viscosity of BIPHS and DCPD than OCN epoxy resin, BIPHS and DCPD have a better peel strength than OCN. The DCPD resin has a better peel strength than BIPHS because of its higher fracture toughness.     

Influence of Zn2+ ion addition on properties of aluminous electrical porcelain

Abstract

ZnO was added as a dopant, in concentrations of 2, 3, and 4 wt-%, to alumina based porcelain batches, in order to study its effect on the fired materials characteristics. An additional composition containing 4 wt-%ZnO and 1 wt-%LiF was also investigated. The results showed that the addition of 4 wt-%ZnO decreased the maturing temperature and improved the electrical properties. It also promoted the development of a mullite phase from the glassy phase. On the other hand, the combination of ZnO and LiF had a negative effect on the electrical properties and on the mullite content. The Li⁺ ions caused the dissolution of mullite crystals and the crystallisation of new phases.     

The Effect of Oily Finish Components on the Adhesion Between Aramid Fibers and Rubber

The use of aramid fibers as a reinforcing material in both tires and mechanical rubber goods, such as hoses, belts, etc., is growing. In these dynamic applications, the adhesion between fiber and rubber is critical. This can be optimized by activating the aramid with an epoxy formulation, followed by RFL (Resorcinol Formaldehyde Latex) treatment. In the past, various combinations of analytical techniques have been used to study the relationship between the fiber surface treatment, the resulting microscopic interphase structure and the macroscopic rubber properties. The fundamental knowledge acquired from these past studies has been exploited here to investigate the effect of oily finish components on the aramid–rubber adhesion. For this purpose, aramid yarn has been treated with various combinations of an adhesion improving (epoxy–amine) component and a processability improving (oily) component. Contrary to general belief, the oily components do not directly reduce the SPAF (Strap Peel Adhesion Force) to rubber, rather show some positive effect. Furthermore, there is a relative broad 'safe' oil range, i.e., fluctuations in the amount of oil will not directly lead to adhesion problems. This is in line with earlier observations, but this study using appropriate analytical techniques provides quantitative confirmation and additional understanding of the fundamental principles behind these effects.     

Effect of the microstructure of copper oxide on the adhesion behavior of epoxy/copper leadframe joints

The thermal oxidation of copper leadframe was carried out at 175°C and the adhesion behavior of the epoxy/copper leadframe joint was analyzed by investigating the microstructure changes of copper oxide with the thermal oxidation time of copper. The peel strength increased sharply at an early stage of oxidation (~20 min) followed by a slight increase. After further oxidation (120 min), the peel strength showed a slight decrease. The contact angles of water and diiodomethane decreased sharply at an early stage of oxidation with negligible change afterwards. As the oxidation time increased, X-ray photoelectron spectroscopy (XPS) results revealed that the chemical composition of copper oxide had changed (Cu/Cu₂O → Cu₂O → CuO); this change improved the wettability of the copper surface, which affected the peel strength. Increase of the surface roughness of copper oxide, investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM), causes the epoxy resin and copper oxide to undergo mechanical interlocking, which increases the peel strength. Failure analysis by SEM and XPS indicated that failure was largely in the copper oxide, and the amount of copper oxide on the peeled epoxy increased as the oxidation time increased, due to the weak mechanical strength of the oxide layer. However, a small portion of the epoxy resin was also fractured during the failure process, regardless of the oxidation time. Consequently, fracture proceeded mainly in the copper oxide close to the epoxy resin/copper oxide interface.     

Deposition and Adhesion Characterization of Ti(BN:MoS2) Based Composite Thin Films Prepared by Closed-Field Unbalanced Magnetron Sputtering

Composite structured solid thin films were deposited on 52100 tool steel by co-sputtering from BN, TiB₂, MoS₂ and Ti targets using a closed-field unbalanced magnetron sputtering process (CFUBMS). The structural and mechanical properties of the composite structured coatings were investigated. The composition and morphology of the films were investigated using X-ray diffraction and scanning electron microscopy (SEM). The adhesion properties of the films were characterized by the use of a Revetest-scratch tester. The adhesion test results indicated that bias voltage was the most effective coating parameter related to the critical load.     

Adhesion and corrosion resistance of epoxy primers used in the automotive industry

One of the most important factors in corrosion prevention by protective coatings is the loss of adhesion of the coating under environmental influence. Thus, adhesion strength is often used when characterizing protective properties of organic coatings on a metal substrate. In this work, the adhesion of different epoxy primers (pigment-free, zinc-rich and chromate-based) was examined on steel. Both the dry and wet adhesion strengths of organic primers were measured directly by a pull-off standardized procedure, as well as indirectly by the NMP test. The corrosion stability of coated samples was investigated by electrochemical impedance spectroscopy. It was shown that under dry test conditions all the samples showed very good adhesion. However, different trends in adhesion for different primers during exposure to the corrosive agent (3% NaCl solution) were observed. The lowest adhesion values were obtained for chromate-based epoxy primer; however, the change in adhesion of this protective system during immersion in 3% NaCl solution for 25 days was the smallest of all investigated samples. Electrochemical impedance measurements in 3% NaCl solution confirmed good protective properties of pigmented epoxy primers on steel, i.e., greater values of pore resistance and charge-transfer resistance, and smaller values of coating capacitance and double-layer capacitance, were obtained for these protective systems.     

Symmetry-based Study of MoS2 and WS2 Nanotubes

The symmetry-based study of MS₂ (M=Mo, W) single-wall nanotubes (SWNTs) is reviewed. First, the structure and symmetry of MS₂ NTs is determined. Then, conserved quantum numbers and general forms of potentials are derived. The valence force-field method implemented into the POLSym code is used to calculate phonon dispersions. Phonons characterized by a zero angular-momentum quantum number are studied in detail. The functional dependence of the frequency of rigid layer modes on NT diameter and chirality are found, and Raman- and infrared-active modes are singled out. Electronic band structure calculations are performed by the symmetry-based density functional tight-binding (DFTB) method. Changes in the band-gap type and size with NT chirality and diameter are evaluated. Optical absorption spectra of individual NTs are calculated using DFTB wave functions for exact transition matrix element calculations. Diffraction patterns of MS₂ are predicted and NT characterization by different diffraction methods is discussed.     

Effect of Curing Procedures on the Electrical Properties of Epoxy-Based Isotropic Conductive Adhesives

The effects of different curing and post-heating treatment procedures on the electrical properties of isotropic conductive adhesives (ICAs) were investigated in this work. The results showed that the bulk resistivity of ICAs cured by multi-step method was lower than that cured by the one-step method, even though they were cured for the same periods. It was also found that the electrical resistance of ICAs continued to decrease during the subsequent post-heating treatment processes. The in situ monitoring the variations in electrical resistance was studied during the curing and post-heating treatment process, and it was found that the cooling process continued to decrease the electrical resistivity of ICAs. The trend of the evidence has been consistent and indicated that the internal stress of ICAs, which depended on the curing and post-heating treatment temperatures, had a significant effect on the electrical resistivity of ICAs. Meanwhile, it was proved that the bulk resistivity of ICAs increased as the internal stress of ICAs weakened by the addition of PEG.     

The role of water in delamination in electronic packages: degradation of interfacial adhesion

Polymeric electronic packages subjected to standard Joint Electron Device Engineering Council (JEDEC) reliability testing are known to exhibit weakening and failures at the polymeric adhesive interfaces. Coupling agents are typically used as additives in epoxy-based materials to improve package reliability. Coupling agent chemistry and environment conditions, including pH, temperature and applied stress, are known factors that affect the rate of adhesion degradation and jeopardize the long-term reliability of the package. In this study, the subcritical interfacial debonding process is described. The debonding rates of polymers with silane, titanate and zirconate coupling agents were characterized at different temperatures by shear fracture tests and tapered double cantilever beam tests under mechanical loading and simultaneous exposure to controlled acidic environments. An analytical procedure was developed to delineate the material parameters governing adhesion degradation. Elevated temperature and acidity were shown to have a strong effect on package reliability, but mechanical loading was found to have a minimal effect on the rate of adhesion degradation. The effects of the JEDEC testing conditions on interfacial bond degradation are discussed using the chemical kinetic model.     

The critical humidity effect in the adhesion of epoxy to glass: role of hydrogen bonding

Adhesion between an epoxy [diglycidyl ether of bisphenol F (DGEBF) cured with diethylene triamine] and glass was lowered abruptly when the epoxy was equilibrated with air whose relative humidity (RH) exceeded a critical value of approximately 70% RH. The critical humidity marking the onset of adhesion loss was also associated with a sudden increase of water uptake by the epoxy. In earlier work, it was shown that this 'transition' was not due to capillary condensation, osmotic cell formation or a decrease in the T _g of the material. Instead, it was speculated that the critical humidity effect was due to the trapping of water by hydroxyl groups which become available as inter-chain hydrogen-bonded structures are broken. To verify the above hypothesis, two model compounds were synthesized. One closely mimicked the cured DGEBF resin and the other had all of its hydroxyl groups replaced by hydrogen. Comparison of the water sorption isotherms of these two model compounds clearly suggested that hydroxyl groups played a key role in the critical humidity effect. Using molecular simulation software, hydrogen bonding between the various polar sites of the hydroxylated model compound was also studied. In the dry state or at low water concentrations, simulations predicted the formation of hydrogen bonds between polar sites. These hydrogen bonds always involved one or more hydroxyl groups. At higher water concentrations, molecular simulations showed that water tended to displace the hydrogen bond network of the epoxy, and in the process, water-mediated 'bridges' between polar groups were formed. The large decrease in entropy associated with the formation of such macrocyclic conformers is thought to be offset by the decreased enthalpy of condensation of water made possible by multiple hydrogen bonding. This suggests that the critical humidity effect might be an 'order-disorder' transition associated with the formation of ring structures closed by hydrogen-bonded water linkages between polar groups. The first-order energetics of this type of transition is consistent with the abrupt nature of the critical humidity effect.     

The Effect of Accelerated Weathering on the Mechanical Properties of Alkali Treated Hemp Fibre/Epoxy Composites

In this study, 65 wt% aligned untreated long hemp fibre/epoxy (AUL) and aligned alkali treated long hemp fibre/epoxy (AAL) composites cured at 70°C using compression moulding were subjected to accelerated weathering using an accelerated weathering chamber with UV-irradiation and water spray at 50°C for four different time periods (250, 500, 750 and 1000 h). After accelerated weathering, tensile strength (TS), flexural strength, Young's modulus (YM), flexural modulus and fracture toughness (K _Ic) were found to decrease and impact energy (IE) was found to increase for both AUL and AAL composites. AUL composite had greater overall reduction in mechanical properties than that for AAL composite upon exposure to accelerated weathering environment. FTIR, TGA and WAXRD analyses of the accelerated weathered composites support the results of the deterioration of mechanical properties upon exposure to accelerated weathering environment.     

Characterization of Ni-Coated WS2 Nanotubes for Hydrodesulfurization Catalysis

A reactivity screening of new nano-hydrodesulfurization (HDS) catalysts was conducted using an ambient pressure flow reactor as well as ultra-high vacuum kinetics techniques. Thiophene was used as a probe molecule. Clean multiwall WS₂ nanotubes (INT-WS₂) as well as Ni- and Co-coated INT-WS₂ were considered. In addition, undoped MoS₂ and Re-doped nanoparticles with fullerene-like structures were studied. Commercial Ni and Co HDS catalysts from Haldor Topsoe (Denmark) as well as “nano MoS₂” from Impex Corp. (USA) were considered as reference materials. The lab-synthesized and commercial systems broke down thiophene into quite similar non-sulfur containing products, as identified by a gas chromatograph. The Ni and Co promoted catalysts showed similar thiophene conversion rates. Although the commercial catalysts had larger thiophene conversion rates than the laboratory-synthesized systems, the Re-doped nano-HDS catalyst showed quite low rates of formation of H₂S, an undesirable by-product.     

A Probe on the Failure Mechanism in Rubber-Modified Epoxy Blends: Morphological and Acoustic Emission Analysis

In this work, diglycidyl ether of bisphenol A based epoxy resin (DGEBA) was modified with varying amounts of two liquid rubbers: carboxyl terminated copolymer of butadiene and acrylonitrile (CTBN); and a hydroxyl terminated polybutadiene (HTPB), using an anhydride hardener. The ultimate aim of this study was to investigate the failure mechanism operating in the rubber-modified epoxies and to evaluate this by correlating these results with the miscibility and interfacial adhesion between the components and the morphology of the cured network. Some of the mechanical and fracture properties, which are associated with the two-phase particulate morphology, were investigated. The visoelastic behavior of modified epoxies was also analyzed and variations in the shift of T _g values in toughened epoxies were explained. The samples were carefully analyzed by an acoustic emission technique to investigate the failure mechanism operating in them. From the response of force and number of acoustic events as well as from the amplitude of acoustic events, we were able to explain the failure mechanisms in the elastomer incorporated epoxy resins supplemented by morphological evidence.     

Properties of Waterborne Polyurethane/CNT Nanocomposite Adhesives: Effect of Countercations

Two series of waterborne polyurethane (WBPU)/carbon nanotube (CNT) nanocomposites were prepared with various CNT contents (0–1.50 wt%). We used a metal-hydroxide (copper hydroxide, Cu(OH)₂) and amine (triethylamine, TEA) as the countercation in the nanocomposites. The interaction of the countercations with the CNTs in the nanocomposite was characterized by TEM, and the interaction effects on the properties, such as the glass transition temperature (T_g), storage modulus, tensile strength, Young's modulus and adhesive strength, were investigated. The CNTs were homogeneously (optimum) dispersed at concentrations of up to 1.25 and 1.00 wt% for the metal-hydroxide and amine series, respectively. At the optimum CNT content, the tensile strength and adhesive strength were maximized in each series. However, the adhesive strength of the WBPU/CNT nanocomposite with the metal-hydroxide countercation was less affected than with the amine-countercation after immersing the adhesive bonded nylon fabrics in water (for up to 48 h).     

Surface reactivity of polyimide and its effect on adhesion to epoxy

Polyimides are commonly used as organic passivation layers for microelectronic devices due to their unique combination of properties such as low dielectric constant, high thermal stability, excellent mechanical properties and superior solvent resistance. Unfortunately, polyimides are well known to be difficult to bond to other materials, especially to epoxy resins. Many surface treatments have been developed to increase epoxy–polyimide adhesion. These treatments include exposure to ion beams, plasmas and chemical solutions. The goal of our research was to relate surface reactivity of epoxy and polyimide resins to the strength of epoxy–polyimide interfaces. The surface reactivity of four polyimides was studied and quantified using contact angle measurements, flow microcalorimetry (FMC), Fourier transform infrared (FT-IR) spectroscopy (using an attenuated total reflection (ATR) accessory) and X-ray photoelectron spectroscopy (XPS). Several ways of analyzing contact angles were tried and only a weak correlation between the polar component or the acid–base components of the surface free energy with the critical interfacial strain energy release rate (i.e., the interfacial fracture strength) was observed. FMC results suggest that the strength of epoxy–polyimide interfaces is related to the molecular interactions between the curing agent and polyimide. The molecular interactions between the curing agent and polyimide surfaces were found to be either greater than epoxy and polyimide interactions or more irreversible. Therefore, the curing agent (2,4-EMI) is thought to play a critical role in controlling adhesion strength.     

The Effect of Tungsten Sulfide Fullerene-Like Nanoparticles on the Toughness of Epoxy Adhesives

In this work the effect of inorganic fullerene-like (closed cages) nanoparticles of tungsten disulfide (IF-WS₂) on the mechanical properties and especially on the toughness of epoxy resins, was studied. The epoxy resin used was the well-known DGEBA (di-glycidyl ether of bis-phenol A) cured with polyamidoamine. The epoxy/IF-WS₂ nanocomposites were prepared by applying a high shear mixing to obtain a uniform dispersion and homogeneous distribution of the IF nanoparticles in the epoxy matrix. Two mixing procedures were used — a low shear of short duration and high shear with a long mixing time. The resulting epoxy nanocomposites were first characterized for their shear and peel strength using appropriate bonded joints. The experimental results demonstrate that enhanced shear strengths and shear moduli were achieved, together with a significant increase in the peel strengths at low concentrations of the IF-WS₂ nanoparticles (more than 100% increase at 0.5 wt% IF-WS₂). Above the threshold value of 0.5% IF-WS₂ the peel strength decreased sharply. The fractured surfaces of the bonded joints were examined by transmission and scanning electron microscopy in order to characterize the fracture mechanisms and analyze the dispersion level of the nanoparticles within the polymer. The electron micrographs indicated that the presence of the nanoparticles in the epoxy matrix induced fracture mechanisms which were different from those observed in the pristine epoxy phase. These mechanisms included: crack deflection; crack bowing; and crack pinning. Evidence for a chemical interaction between the nanoparticles and the epoxy were obtained by infrared measurements in the attenuated total transmittance mode. The data suggests the formation of new carbon–oxygen–sulfur bonds, which are most likely due to the reaction of the outermost sulfur layer of the IF nanoparticles with the reactive epoxy groups. The observed simultaneous increase in both shear and peel strengths at very low IF-WS₂ concentrations, found in this work, could lead to the development of high performance adhesives and to new types of structural and ballistic fiber nanocomposites.